US4457859A - Mesomorphic material containing 2,2'-azoimidazole compounds containing 1,1'-benzylideneamino substituents - Google Patents

Mesomorphic material containing 2,2'-azoimidazole compounds containing 1,1'-benzylideneamino substituents Download PDF

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Publication number
US4457859A
US4457859A US06/364,848 US36484882A US4457859A US 4457859 A US4457859 A US 4457859A US 36484882 A US36484882 A US 36484882A US 4457859 A US4457859 A US 4457859A
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United States
Prior art keywords
azoimidazole
mesomorphic
mesomorphic material
compound
dichroism
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Expired - Fee Related
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US06/364,848
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English (en)
Inventor
Alexandr V. Ivaschenko
Valentina T. Lazareva
Elena K. Prudnikova
Vladimir G. Rumyantsev
Tamara S. Pljusnina
Viktor A. Nefedov
Lev M. Blinov
Viktor V. Titov
Vladimir P. Sevostyanov
Vadim M. Shoshin
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Priority claimed from SU802967844A external-priority patent/SU951856A1/ru
Priority claimed from SU802967265A external-priority patent/SU946186A1/ru
Priority claimed from SU802967803A external-priority patent/SU944323A1/ru
Application filed by Individual filed Critical Individual
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Publication of US4457859A publication Critical patent/US4457859A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
    • C09K19/3477—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a five-membered aromatic ring containing at least one nitrogen atom
    • C09K19/348—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom the heterocyclic ring being a five-membered aromatic ring containing at least one nitrogen atom containing at least two nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/60—Pleochroic dyes
    • C09K19/601—Azoic

Definitions

  • the present invention relates to novel dichroic dyestuffs for liquid crystals and, more specifically, to 2,2'-azoimidazole derivatives, a method for preparing same, a mesomorphic material and an electrooptical device.
  • 2,2'-azoimidazole derivatives currently known is 1,1'-bisbenzylideneamino-4.4'-diphenyl-2,2'-azoimidazole described in FRG Journal (Chem.Ber., vol.101, September 1968, Verlag Chemie, Valgheim, Beyer A., Hetzheim, H. Honeck, D. Linq, T. Pyl "Synthesis of Novel Imidazole Derivatives", p.3151-3162).
  • Dyestuffs with a negative dichroism under the above-specified conditions give a reverse picture and a combination of dyestuffs with positive and negative dichroism makes it possible to obtain colour shifting in the electrooptical device, provided that these dyestuffs have spectrally spaced absorption bands within the visible region of spectrum.
  • dyestuffs with a positive dichroism are known in a sufficiently broad range
  • dyestuffs with a negative dichroism which are of a practical interest are limited to tetrazine derivatives (cf.French Pat. Nos. 2,416,253; 2,422,707, 2,428,666 Cl. C 09 K 3/34, published 1978, 1978 and 1979 respectively).
  • this dyestuff has, on the one hand, absorption bands located in the visible area of spectrum such that their position does not ensure the contrast required for a human eye. Furthermore, this dyestuff makes it possible to obtain, in an electrooptical device, light signs against a dark background which is also unsatisfactory for perception by a human eye.
  • Dyestuffs for mesomorphic materials having two spectrally spaced absorption bands within the visible area of spectrum, so that the long-wave band has a negative dichroism and the short-wave band has a positive dichroism, are not known at all.
  • the present invention is directed to the provision of novel 2,2'-azoimidazole derivatives having two spectrally spaced absorption bands in the visible part of their spectrum wherein the long-wave band has a negative dichroism in a mesomorphic material and the short-wave band--a positive dichroism; the invention is also directed to the provision of a method for preparing these 2,2'-azoimidazole derivatives and, creation, on their basis, of a mesomorphic material or liquid crystal and an electrooptical device.
  • 2,2'-Azoimidazole derivative of the general formulae I and II have two spectrally spaced absorption bands in the visible spectrum area so that the long-wave band has a negative dichroism and the short-wave-a positive one.
  • the structure of the novel compounds of the general formulae I and II is justified by the data of elemental analysis, electron spectra and dichroism or absorption bands measured in a mesomorphic matrix.
  • the long-wave absorption bands are biased bathochromically as compared to corresponding bands in electron spectra of cis-2,2'-azoimidazoles of the general formula II.
  • the above-mentioned mesomorphic material can also contain 0.3 to 3.0% by weight of a dyestuff possessing a positive dichroism.
  • the dyestuff with a positive dichroism a blue or green dyestuff with a positive dichroism.
  • the mesomorphic material according to the present invention has two absorption bands in the visible part of spectrum and the long-wave band has a negative, and the short-wave band--a positive dichroism.
  • a mesomorphic material contains the above-mentioned dyestuff with a positive dichroism, in this case it has three absorption bands in the visible part of spectrum so that the long-wave and short-wave bands have a positive dichroism, while the medium-wave band has a negative dichroism.
  • the material according to the present invention reveals either a common effect or a cholesteric effect of the "guest-host" type and enables colour switching-over in an electrooptical device.
  • a dichroic working body comprising a layer of the above-specified mesomorphic material positioned between transparent electrodes provided with a source of voltage control; this working body has two absorption bands within the visible part of spectrum so that the long-wave band manifests a negative dichroism and the short-wave band--a positive one.
  • the mesomorphic material contains a working body incorporating, a dyestuff with a positive dichroism
  • the working body has three absorption bands in the visible part of spectrum so that the long-wave and short-wave bands have a positive dichroism, while the medium-wave band has a negative dichroism.
  • the electrooptical device according to in invention is useful for the presentation and processing of information.
  • the present invention is concerned mainly with the provision of novel 2,2'-azoimidazole derivatives corresponding to general formulae I and II.
  • the 2,2'-azoimidazole derivatives according to the present invention corresponding to formula I or II should be produced by reacting an appropriate solution of 2-amino-1-arylideneaminoimidazole of formula III in an aromatic hydrocarbon with manganese dioxide upon heating with azeotropic distillation of water formed in the reaction for 2 to 4 hours, followed by filtration of the reaction mass to remove manganese salts and cooling the thus obtained solution, with a subsequent isolation of the desired product by conventional techniques. This method is the most convenient in practicing of the present invention.
  • the desired products prepared according to the present invention can be isolated from the reaction mass by any methods known in the organic chemistry such as evaporation of the reaction solution resulting from separation of manganese salts, recrystallization of the residue or chromatographic treatment of the above-mentioned solution, or by any other methods.
  • the mesomorphic matrix should preferably have a positive dielectric anisotropy and maximum possible temperature range of the nematic mesophase, room temperature inclusive. This material makes it possible to obtain, in electrooptical systems for presentation and processing of information based on the use of the "guest-host" effect violet signs against a light-brown background with a high contrast of the image on the whole.
  • the mesomorphic material according to the present invention comprises a mesomorphic matrix consisting of one or more mesomorphic compounds.
  • mesomorphic substances may pertain to both the same homologous series of substances and to different homologous series and classes of substances such as azoxybenzene derivatives, diphenyl derivatives, phenylbenzoate derivatives, Schiff's bases and the like.
  • This device is successfully useful in various electrooptical and optoelectronic systems for information presentation and processing, for example in electronic watch, computers, different information displays, light valves, advertizing tableaux and the like.
  • Examples 1 to 6 The methods for preparing these compounds are illustrated by Examples 1 to 6, Examples 7 to 14 illustrate the mesomorphic material according to the present invention and Examples 15 to 20 illustate the electrooptical device.
  • Chloroform is distilled-off in vacuum and the residue is recrystallized from a minimum amount of ethanol to give 38 g of 4-bromoacetyl-4'-octylbiphenyl; from 19.6 g of the product and 16.5 g of benzaldehydeguanylhydrazone there is obtained, following the procedure of Example 1, 0.65 g of 1,1'-bisbenzylideneamino-4,4'-di-[4-(4-octylphenylene)-phenylene]-2,2'-azoimidazole (II /3/).
  • Table 1 hereinbelow.
  • Table 2 shows the data on dichroism of longwave absorption bands of novel derivatives of 2,2'-azoimidazole of the general formulae I and II measured in an oriented mesomorphic matrix consisting of n-cyanophenyl esters of n-alkylbenzoic and n-alkylcinnamic acids.
  • Use is made of a working body interposed between electrodes and containing 99% by weight of a liquid crystal GK-1 with positive dielectric anisotropy and 1% by weight of a dyestuff II(I) or II(6) having two absorption bands with a width of 100-140 nm and maximum near 390-400 nm and 530 nm within the visible range of spectrum; the former out of the above-mentioned bands has a positive dichroism, the latter--negative one.
  • the starting orientation of the working body with the width of 20 ⁇ m in planar or twisted to 90° (“twist"-structure), and its colour for polarized light is yellow or yellowish-orange.
  • Applied to the electrodes is an electric field with the frequency of 20 Hz and intensity of 5 ⁇ 10 V/cm.
  • a homeotropic structure with a crimson colour is obtained.
  • a working body consisting of 0.7% by weight of DK-3, 12% by weight of cholesteric liquid crystal of cholesteryl chloride and 87.3% by weight of a liquid crystal with a posititive dielectric anisotropy GK-3.
  • the starting texture of the working body having thickness of 20 ⁇ m is planar and of yellow colour.
  • the electric field with the frequency of 200 Hz is applied to the electrodes, the field intensity being 10 4 V/cm.
  • a homeotropic structure of a crimson colour is obtained. The colour switching-over in this case is observed without a polaroid.
  • novel 2,2'-azoimidazole derivatives of the general formulae I and II according to the present invention is useful in the manufacture of mesomorphic materials to be used in electrooptical devices for information presentation and processing widely employed in electronics.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Liquid Crystal (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Liquid Crystal Substances (AREA)
US06/364,848 1980-07-31 1981-06-25 Mesomorphic material containing 2,2'-azoimidazole compounds containing 1,1'-benzylideneamino substituents Expired - Fee Related US4457859A (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
SU2967265 1980-07-31
SU2967803 1980-07-31
SU802967844A SU951856A1 (ru) 1980-07-31 1980-07-31 Жидкокристаллический материал
SU2967844 1980-07-31
SU802967265A SU946186A1 (ru) 1980-07-31 1980-07-31 Производные 2,2-азоимидазола как дихроичные красители дл жидких кристаллов
SU2967311 1980-07-31
SU2967311 1980-07-31
SU802967803A SU944323A1 (ru) 1980-07-31 1980-07-31 Дихроичный краситель дл жидкокристаллического материала

Publications (1)

Publication Number Publication Date
US4457859A true US4457859A (en) 1984-07-03

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US (1) US4457859A (enrdf_load_html_response)
JP (1) JPS57501238A (enrdf_load_html_response)
CH (1) CH651844A5 (enrdf_load_html_response)
DE (2) DE3152228A1 (enrdf_load_html_response)
FR (1) FR2487830A1 (enrdf_load_html_response)
GB (1) GB2095273B (enrdf_load_html_response)
NL (1) NL8120400A (enrdf_load_html_response)
WO (1) WO1982000472A1 (enrdf_load_html_response)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908363A (en) * 1987-03-20 1990-03-13 Hoffmann-La Roche Inc. Imidazole derivatives
GB2393185A (en) * 2002-09-17 2004-03-24 Generics Preparation of azo compounds by oxidation dimerisation of 1 or 2 aromatic amines, and use thereof to prepare 3,3'-azo-bis(6-hydroxybenzoic acid) & its esters
GB2396154A (en) * 2002-10-15 2004-06-16 Merck Patent Gmbh 4,5-Dicyanoimidazole derivatives and their use in liquid crystal media and liquid crystal devices

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5289301A (en) * 1992-06-12 1994-02-22 Boit, Inc. Liquid crystal color modulation displays with dyes of different orders and circuitry for providing modulated AC excitation voltage

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE564813C (de) * 1930-06-04 1932-11-23 Siemens Schuckertwerke Akt Ges Buerstenabhebevorrichtung fuer Buerstenhalter elektrischer Maschinen
US3646040A (en) * 1968-01-31 1972-02-29 Bayer Ag Process for the preparation of dialkylpyridines

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR966395A (fr) * 1948-05-12 1950-10-09 Prod De Chimie Organique De La Procédé de préparation de composés de la série des thio-hydantoïnes et produits nouveaux de cette série
CH564813A5 (enrdf_load_html_response) * 1973-11-12 1975-07-31 Bbc Brown Boveri & Cie
EP0002104B1 (en) * 1977-10-14 1982-10-20 BDH Chemicals Limited Pleochroic dyes suitable for use in solution with liquid crystal materials for electro-optic device applications
DD137242B1 (de) * 1978-06-16 1980-10-29 Dietrich Demus Nematische kristallin-fluessige mischungen
CH641828A5 (fr) * 1979-08-17 1984-03-15 Ebauches Sa Composition a base de cristal liquide pour dispositif electro-optique.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE564813C (de) * 1930-06-04 1932-11-23 Siemens Schuckertwerke Akt Ges Buerstenabhebevorrichtung fuer Buerstenhalter elektrischer Maschinen
US3646040A (en) * 1968-01-31 1972-02-29 Bayer Ag Process for the preparation of dialkylpyridines

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Chemische Berichte Herausgegeben Von, with translation, Der Gesellschaft Deutscher Chemiker, 101 Jahrgang, Heft 9/1968, SS. 3151 3162, with translation, (Beyer et al.). *
Chemische Berichte Herausgegeben Von, with translation, Der Gesellschaft Deutscher Chemiker, 101 Jahrgang, Heft 9/1968, SS. 3151-3162, with translation, (Beyer et al.).
L. M. Blinov Electro and Magnetooptics of Liquid Crystals, (Moscow, Nauka , Publishers, Chief Editorial Board for Physico Mathematical Literature, 1978, pp. 148 152), with translation. *
L. M. Blinov-Electro-and Magnetooptics of Liquid Crystals, (Moscow, "Nauka", Publishers, Chief Editorial Board for Physico-Mathematical Literature, 1978, pp. 148-152), with translation.

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4908363A (en) * 1987-03-20 1990-03-13 Hoffmann-La Roche Inc. Imidazole derivatives
GB2393185A (en) * 2002-09-17 2004-03-24 Generics Preparation of azo compounds by oxidation dimerisation of 1 or 2 aromatic amines, and use thereof to prepare 3,3'-azo-bis(6-hydroxybenzoic acid) & its esters
GB2393185B (en) * 2002-09-17 2005-10-12 Generics A novel process for the preparation of 3,3'-azo-bis(6-hydroxybenzoic acid) and its derivatives
GB2396154A (en) * 2002-10-15 2004-06-16 Merck Patent Gmbh 4,5-Dicyanoimidazole derivatives and their use in liquid crystal media and liquid crystal devices
GB2396154B (en) * 2002-10-15 2007-02-28 Merck Patent Gmbh 4,5-Dicyanoimidazole derivatives and their use in liquid crystal media and liquid crystal devices

Also Published As

Publication number Publication date
FR2487830A1 (fr) 1982-02-05
CH651844A5 (de) 1985-10-15
DE3152228C1 (de) 1985-07-18
WO1982000472A1 (en) 1982-02-18
GB2095273B (en) 1984-09-19
GB2095273A (en) 1982-09-29
DE3152228A1 (de) 1983-01-13
FR2487830B1 (enrdf_load_html_response) 1983-01-28
JPS57501238A (enrdf_load_html_response) 1982-07-15
NL8120400A (enrdf_load_html_response) 1982-06-01

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